The synthesis, physicochemical, and optoelectronic properties of a new class of low band-gap (approximate to 1.3 eV) donor-acceptor copolymers based on a highly electron-deficient meso-5-(2-octyldodecyl)thiophene-substituted BODIPY pi-unit are presented. The polymeric solutions exhibit strong aggregation-dependent excitonic properties indicating the presence of enhanced pi-coherence as a result of strong interchain interactions. The polymeric semiconductor thin films prepared by spin coating show isotropic nodule-like grains with essentially no ordering in the out-of-plane direction. Field-effect hole mobilities of 0.005 cm(2) V-1.s(-1) are observed in bottom-gate top-contact organic field-effect transistors, and inverted bulk-heterojunction organic photovoltaics employing the polymer:PC71BM active layer exhibit excellent power conversion efficiencies of 6.2% with a short-circuit current of 16.6 mA cm(-2). As far as it is known, this is a record high value achieved to date for a boron-containing donor polymer in the photovoltaic literature indicating a significant enhancement in power conversion efficiency (>3-4 times). The findings clearly present that rationally designed BODIPY-based donor-acceptor copolymers can be a key player in photovoltaic applications.